Multicomponent Distillation  Key components
The feed components are listed in order of their relative
 need more than one distillation tower, for n
components, n-1 fractionators are required
 Specification Limitations
The following are established at the beginning
1. Temperature, pressure, composition, and rate of
the feed.
2. Pressure of the distillation
3. Feed to be introduced on that tray which will
result in the least total number of trays
(optimum feed-tray location)
4. Heat loses (even if assumed to be zero)
Under these circumstances only three additional items of
the following list need to be specified, any other items
must be calculated.
1. Total number of trays.
2. Reflux ratio
3. Reboil ratio (ratio of vapor produced by the
reboiler to residue withdrawn)
4. Concentration of one component in one product
(a maximum of two may be chosen)
5. Ratio of flow of one component in the distillate
to the flow of the same component in the
residue, or split of the component (a maximum
of two may be chosen)
6. Ratio of total distillate to total residue
108
volatility. The more volatile components are called
light, the less volatile are heavy. The components
separated in a tower are called light key (more volatile)
and heavy key (less volatile). Any components lighter
than the light key are called light components, while
those heavier than the heavy key are called heavy
components.
In hydrocarbon systems, because of nonidealities, the
equilibrium data are often represented by
yA = KAxA, yB= KBxB, yC = KCxC, yD = KDxD
where KA is the vapor-liquid equilibrium constant or
distribution coefficient for component A. K is a function
of temperature and pressure, but is assumed to be
independent of composition, which is sufficiently
accurate for most engineering calculations. For an ideal
system, KA = PA*/PT = vapor pressure/total pressure.
The relative volatility in multicomponent distillation is
always computed with respect to the heavy key
K y /x
 j  j  je je (1)
K hk yhke / x hke
The value of  is greater than 1 for any component
lighter than the heavy key and less than 1 for any heavier
component.
109
 Bubble-point and dew-point calculations Component Pi* at 105oC, Ki = Pi*/1.2 xi yi=Kixi
These are required for a flash distillation and for each atm
stage of a multicomponent distillation, calculated by 1. Hexane 2.68 2.23 0.33 0.7359
trial-and -error. 2. Heptane 1.21 1.01 0.37 0.3737
NC NC
For the bubble point,  yi   Ki xi 1. 0 (2) 3. Octane 0.554 0.462 0.30 0.1386
i 1 i 1 ∑ = 1.248
NC NC yi
For the dew point,  xi   1. 0 (3)
i 1 i 1 Ki Since ∑yi is too large, try a lower temperature. Since the
First a temperature is assumed and the values of Ki are major contribution is from the first term, try a
obtained from literature. If the summation  1 choose temperature where Ki is lower by a factor of 1/1.24,
another temperature. 2.68/1.24=2.16. Choose T = 96oC, where P1* = 2.16 atm.

Example D9. Find Component Pi* at Ki = xi Kixi yi

the bubble-point and 96oC, atm Pi*/1.2
the dew-point 1. Hexane 2.16 1.8 0.33 0.5940 0.604
temperatures and the 2. Heptane 0.93 0.775 0.37 0.2868 0.292
corresponding vapor 3. Octane 0.41 0.342 0.30 0.1025 0.104
and liquid ∑ = 0.9833 1.000
compositions for a
mixture of 33 mole % This is a liitle bit small. Try another T = 97oC, close
n-hexane 37 mole % enough to 96oC so that y .
∑
n-heptane and 30
mole % n-octane at 1.2
atm total pressure. Dew point. The dew point is higher than the bubble point,
Solution. The logP vs so use 105oC as a first guess.
T plot is shown as Component Ki yi yi / Ki
right. 1. Hexane 2.23 0.33 0.148
2. Heptane 1.01 0.37 0.366
Bubble point. Guess T = 105oC, this is based on the 3. Octane 0.462 0.30 0.649
vapor pressure of heptane, the middle component, is 1.2 ∑ = 1.163
atm.
110 111
Since the sum is too high, try a higher temperature, T = Example D10. The mixture of example D9 is
110oC. subjected to a flash distillation at 1.2 atm pressure, and
Component Pi* at Ki = yi yi /Ki xi 60% of the feed is vaporized.
o
110 C Pi*/1.2 (a) Find the temperature of the flash and the
1. Hexane 3 2.5 0.33 0.132 0.130 composition of the liquid and vapor products.
2. Heptane 1.38 1.15 0.37 0.3217 0.317 (b) To what temperature must the feed liquid be
3. Octane 0.64 0.533 0.30 0.5625 0.553 heated for 60% vaporization on flashing?
∑ = 1.0162 1.000 Solution.
By extrapolation, the dew point is 110.5oC, and the (a) The flash temperature must lie between the bubble
composition of the liquid in equilibrium with the vapor point (97oC) and the dew point (110.5oC).
is calculated by x
/ /
. Assume T = 97+0.6(110.5-97) = 105 oC.
∑ / . From the figure in example D9, K1 =2.68/1.2=2.23,
K2 =1.21/1.2=1.01, K3 =0.554 /1.2=0.462.
 Flash distillation The value of f is 0.6.

Material balance for component i gives The right hand side of Eq. (6) becomes
f 1 x . . .
yDi  x Bi  Fi (4)
f f . . . . . .
where f=V/F is the fraction of the feed vaporized, yDi is =0.190+0.368+0.443=1.001
in equilibrium with xBi. So yDi  Ki x Bi , substitute this
into Eq. (4) and solve for xBi. This is close to unity so the flash temperature is 105 oC.
x Fi The composition of the liquid product is 19% n-hexane,
x Bi  (5) 36.8% n -heptane and 44.2% n -octane.
f  K i  1  1
The summation on xBi should be unity. The composition of the vapor product is computed from
NC NC xFi
 xBi  1   (6) the values of K and x.
i 1 i 1 f  K i  1  1 n-hexane, y = 0.190(2.23) = 0.424
This equation is again solved by iteration. The final n –heptane, y = 0.368(1.01) = 0.372
values of T and Ki are used to calculate the composition n –octane, y = 0.443(0.462) = 0.204
of the top and bottom product streams. 1.000

112 113
(b) To determine the temperature of the feed before  Total Reflux for multicomponent distillation
flashing, an enthalpy balance is made using 105 oC as the (Minimum stages for total reflux)
reference temperature. The heats of vaporization at 105
o
C and the average heat capacities of the liquid from 105 For binary distillation, if the relative volatility of the two
to 200 oC are obtained from the literature. components is approximately constant, we have the
Cp, cal/(mol K) ΔHv, cal/mol following Fenske equation to calculate the minimum
n-hexane 62 6370 number of theoretical steps when a total condenser and a
n –heptane 70 7510 reboiler are used.
n –octane 78 8560  x 1  xB 
ln D 
1 
Nm   B 
x D x
Based on liquid at 105 oC, the enthalpies of the product 1 (7)
ln  AB
are
Hvapor = 0.6(0.424x6370+0.372x7510+0.204x8560) Similarly for any two components (i & j) in
= 4345 cal multicomponent distillation,
Hliquid = 0 x / x 
ln Di Bi 
 x Dj / x Bj 
For the feed, Nm  1 (8)
ln  ij
C 0.33x62 0.37x70 0.30x78
 ij  3  Dij Fij Bij (9)
69.8 cal/ mol °C
Hence, 69.8(T0 – 105) = 4345 The subscripts D, F and B in Eq. (9) refer to the
T0 = 167oC = preheat temperature temperatures of the distillate, feed plate, and bottoms in
the column. Nm is the minimum number of equilibrium
stages excluding the reboiler, at total reflux.

The Fenske equation is derived as below. At total

reflux, D = B = 0, so V = L. Consider the equilibrium
partial reboiler for any two components A and B,
y /x
α
y /x
Rearrange to obtain
114 115
 If we define αAB as the geometric average relative
α (10)
volatility,
Material balances for these two components around the α α α …α α α / (18)
reboiler are Eq. (17) becomes
VRyA,R = LNxA,N (11a)
VRyB,R = LNxB,N (11b) α (19)
Since VR = LN for total reflux (B = 0), we have Solving Eq. (19) for Nm, we have
yA,R = xA,N, yB,R = xB,N (at total reflux) (12) /
Combining Eqs. (10) and (12), /
N 1 (20)
α (13)
or
If we move up the column to stage N, the equilibrium is /
/
α (14) N 1 (21)

The mass balances around stage N simplify to

yA,N = xA,N-1 and yB,N = xB,N-1 The fractional recovery of A in the distillate is
Combining these equations to give FR (22)
α (15) The fractional recovery of A in the bottoms is
Eqs. (13) and (15) can be combined to give FR 1 FR (23)
α α (16) Hence
Dx FR Fx (24)
Which relates the ratio of liquid mole fractions leaving Bx 1 FR Fx (25)
stage N-1 to the ratio in the reboiler.
The Fenske equation can also be written as
Repeating this procedure until we reach the top stage, we /
have /
N 1 (26)
α α …α α α (17)

116 117
Example D11. A mixture with 33% n-hexane, 37% n- at the flash temperature were taken from the previous
heptane, and 30% n-octane is to be distilled to give a example.
distillate product with 0.01 mole fraction n-heptane and  Lk,HK  2.23 / 1.01  2.21
a bottoms product with 0.01 mole fraction n-hexane.  x D,LK / x B,LK 
The column will operate at 1.2 atm. 60% of the feed is ln   0.99 / 0.01 
ln  
vaporized. Calculate the complete product x /
 D,HK B,HK  x  0.01 / 0.544 
Nm  1  1
compositions and the minimum number of ideal plates at ln  LK , HK ln 2.21
infinite reflux.  10.8  1  9.8
So the minimum number of ideal stages is 9.8 plus a
Solution reboiler.
light key (LK) heavy key (HK) heavy nonkey (HNK)
n-hexane n-heptane n-octane A more accurate estimate of Nm can be obtained using a
Assume no n-octane and 0.99 mole fraction n-hexane in mean relative volatility based on the values at the top,
the distillate. Take 100 mol/h of feed as the basis middle, and bottom of the column. The top
overall M.B. F = D + B = 100 o
temperature is about 75 C, the boiling point of n-hexane
hexane M.B. FxF = DxD + BxB at 1.2 atm, and the relative volatility is 2.53. The
100x0.33 = 0.99D+(100-D)(0.01) bottom temperature is about 115oC by using a bubble
D=32/0.98=32.65 mol/h; B=100-D = 67.35 mol/h point calculation for the bottoms product, giving a
The composition of the bottoms product can be relative volatility of 2.15.
calculated since this stream contains all the octane, all  LK , HK  3 2.53 2.21 2.15  2.29
but 0.01D of the heptane, 0.01 mole fraction of hexane. Hence, Nm =9.4
FxF DxD xD BxB xB K at 105oC,
1.2 atm
To check our assumption of no octane in the distillate,
LK n-C6 33 32.32 0.99 0.68 0.010 2.23
the Fenske equation can be applied to heptane and
HK n-C7 37 0.33 0.01 36.67 0.544 1.01
HNK n-C8 30 0 0 30 0.446 0.462 octane using  = K2/K3 = 1.01/0.462 = 2.19:
D=32.65 B=67.35  0.01 / 0.544 
ln 
Use the Fenske equation to obtain the minimum number  x D3 / 0.446 
of plates. The relative volatility of the light key to the N m  1  10.4 
ln 2.19
heavy key is the ratio of their K factors. The K values from which xD3 = 2.4x10-6, which is negligible.

118 119
 Minimum Reflux Ratio for 2. Underwood method
multicomponent distillation By using constant average ’s and assuming
constant molal overflow (L/V), the following
At this reflux ratio, the desired separation is just two equations are solved to obtain RDm:
 i x Fi
barely possible, but an infinite number of plates is 1 q   (28)
required. The desired separation is usually refers i  
Vmin x
to the amount of light key recovered in the distillate  R Dm  1   i Di (29)
and the amount of heavy key recovered in the D i  
bottoms. where q is the moles of liquid to stripping section
of column per mole of feed,  is a parameter to be
Since the only purpose of obtaining the minimum found from Eq. (28). The correct value of 
reflux ratio is to estimate the product compositions should lie between the values of  for the keys.
at RDm and to ensure that the specified RD is
reasonable, an exact value is not required. There
are two approximation methods in estimating RDm:

1. Treating the mixture as a pseudobinary

(light & heavy keys)
L min  Dx D,LK / Fx F,LK    LK,HK  Dx D,HK / Fx F,HK 

F  LK,HK  1
(27)

120 121
Example D12. A mixture with 4% n-pentane, (a) By using the pseudobinary method, we have
40% n-hexane, 50% n-heptane, and 6% n-octane is L min 39.2 / 40  2.48(0.5 / 50)
  0.645
to be distilled at 1 atm with 98% of the hexane and F 2.48  1
1% of the heptane recovered in the distillate. L min L min F 1
What is the minimum reflux ratio for a liquid feed R Dm    0.645  1.48
D F D 0.437
at the boiling point?
(b) By using the Underwood method, the K values at 80
o
Solution C are converted to relative volatilities and the  value
The light key is n-hexane and the heavy key is n- between 1 and 2.48 is found by trial. Since q=1 (feed
heptane. The other components are sufficiently at the boiling point), we should have
different in volatility to be undistributed. The x
 i Fi  1  q  1  1  0
known information is summarized below (assume i  
100 moles of feed).
i xFi  i x Fi  i x Fi
 , =1.5  , =1.48
xF FxF DxD xD BxB xB i   i  
n-C5 0.04 4 4 0.092 0 0 n-C5 6.46 0.040.052 0.052
LK n-C6 0.40 40 39.2 0.897 0.8 0.014 n-C6 2.48 0.401.012 0.992
HK n-C7 0.50 50 0.5 0.011 49.5 0.879 n-C7 1.0 0.50-1.00 -1.042
n-C8 0.06 6 0 0 6 0.107 n-C8 0.41 0.06
D=43.7 B=56.3 -0.023 -0.023
0.041 -0.021
K80oC KxF The bubble point of the feed is By further trials or interpolation, =1.487, so
n-C5 3.62 0.145 obtained by checking the
n-C6 1.39 0.556  i x Di 6.64(0.092) 2.48(0.897) 1(0.011)
NC NC R Dm  1     
n-C7 0.56 0.280 equation  y Fi   K i x Fi 1.0 , this  i   6.64  1.487 2.48  1.487 1  1.487
n-C8 0.23 0.014 i 1 i 1
temperature is found to be 80 oC. = 0.119 + 2.24 - 0.023 = 2.336
The corresponding LK, HK is 1.39/0.56 = 2.48.
RDm = 1.34, which is 10% less than the value
obtained using pseudobinary method.

122 123
 Number of ideal plates at operating reflux Example D13. Estimate the number of ideal
(Gilliland correlation) plates required for the separation specified in
Example D11, if the reflux ratio is 1.5RDm.
Gilliland proposed a simple empirical method to
estimate the number of plates in multicomponent Solution
distillation. The correlation requires knowledge From Example D11, the minimum number of ideal
only of the minimum number of plates at total stages is 9.4 plus a reboiler, or 10.4. The value of
reflux and the minimum reflux ratio. The RDm is obtained by the Underwood method.
correlation is given below. xF xD K 
LK n-hexane 0.33 0.99 2.23 2.21
HK n-heptane 0.37 0.01 1.01 1.0
n-octane 0.30 0 0.462 0.457
For a saturated liquid feed, q=1,
 i x Fi
  1 q  11  0
i  
By trial, =1.45,
 i x Di 2.21(0.99) 1.0(0.01)
R Dm  1      2.86
 i   2.21  1.45 1  1.45
RDm = 1.86, RD = 1.5x1.86 = 2.79
R D  R Dm 2.79  1.86
  0.245
RD 1 2.79  1
From the Gilliland correlation,
N  N min
 0.41
N 1
N - 10.4 = 0.41N + 0.41
N is the total number of plates in the system, N = 10.81/0.59 = 18.3 stages, including the reboiler
including the reboiler. The same for Nmin.
124 125